Working fluid for heat cycle, composition for heat cycle system, and heat cycle system

ABSTRACT

To provide a working fluid for heat cycle having a low global warming potential and having high durability, which can replace R410A, a composition for a heat cycle system comprising it, and a heat cycle system employing the composition.A working fluid for heat cycle, which contains trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane, wherein the proportion of the total amount of trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane based on the entire amount of the working fluid is higher than 90 mass % and at most 100 mass %, and based on the total amount of trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane, the proportion of trifluoroethylene is at least 10 mass % and less than 70 mass %, the proportion of 2,3,3,3-tetrafluoropropene is at most 50 mass %, and the proportion of difluoromethane is higher than 30 mass % and at most 75 mass %.

TECHNICAL FIELD

The present invention relates to a working fluid for heat cycle, acomposition for a heat cycle system comprising the working fluid, and aheat cycle system employing the composition.

BACKGROUND ART

In this specification, abbreviated names of halogenated hydrocarboncompounds are described in brackets after the compound names, and inthis specification, the abbreviated names are employed instead of thecompound names as the case requires.

Heretofore, as a working fluid for heat cycle such as a refrigerant fora refrigerator, a refrigerant for an air-conditioning apparatus, aworking fluid for power generation system (such as exhaust heat recoverypower generation), a working fluid for a latent heat transport apparatus(such as a heat pipe) or a secondary cooling fluid, a chlorofluorocarbon(CFC) such as chlorotrifluoromethane or dichlorodifluoromethane or ahydrochlorofluorocarbon (HCFC) such as chlorodifluoromethane has beenused. However, influences of CFCs and HCFCs over the ozone layer in thestratosphere have been pointed out, and their use is regulated atpresent.

Under the above conditions, as a working fluid for heat cycle, ahydrofluorocarbon (HFC) which has less influence over the ozone layer,such as difluoromethane (HFC-32), tetrafluoroethane or pentafluoroethane(HFC-125) has been used, instead of CFCs and HCFCs. For example, R410A(a pseudoazeotropic mixture refrigerant of HFC-32 and HFC-125 in a massratio of 1:1) is a refrigerant which has been widely used. However, itis pointed out that HFCs may cause global warming.

R410A has been widely used for a common air-conditioning apparatus suchas a so-called package air-conditioner or room air-conditioner, due toits high refrigerating capacity. However, it has a global warmingpotential (GWP) of so high as 2,088, and accordingly development of aworking fluid with low GWP has been desired. Further, development of aworking fluid has been desired on the condition that R410A is simplyreplaced and existing apparatus will be used as they are.

In recent years, a hydrofluoroolefin (HFO) i.e. a HFC having acarbon-carbon double bond is expected, which is a working fluid havingless influence over the ozone layer and having less influence overglobal warming, since the carbon-carbon double bond is likely to bedecomposed by OH radicals in the air. In this specification, a saturatedHFC will be referred to as a HFC and distinguished from a HFO unlessotherwise specified. Further, a HFC may be referred to as a saturatedhydrofluorocarbon in some cases.

2,3,3,3-Tetrafluoropropene (HFO-1234yf) is known as a working fluidhaving a low global warming potential (GWP). However, althoughHFO-1234yf has a high coefficient of performance, its refrigeratingcapacity is low as compared with R410A, and it cannot be used forconventional air-conditioning apparatus, etc., for which R410A has beenused, such as a so-called package air-conditioner and roomair-conditioner.

As a working fluid employing a HFO, for example, Patent Document 1discloses a technique relating to a working fluid usingtrifluoroethylene (HFO-1123) which has the above properties and withwhich excellent cycle performance will be obtained. Patent Document 1also discloses an attempt to obtain a working fluid comprising HFO-1123and various HFCs in combination for the purpose of increasing the flameretardancy, cycle performance, etc. of the working fluid.

It has been know that HFO-1134yf is useful as a HFO to be used for aworking fluid for heat cycle, and a technique relating to HFO-1234yf hasbeen developed. For example, Patent Document 2 discloses compositionscontaining HFO-1234yf obtainable in production of HFO-1234yf by aspecific process. There are many compositions disclosed in PatentDocument 2, and compositions containing HFO-1234yf and HFO-1123 areincluded. However, HFO-1123 is disclosed only as a by-product ofHFO-1234yf together with many other compounds, and Patent Document 2failed to disclose use of a composition containing the two in a specificproportion as a working fluid and that the composition has excellentcoefficient of performance and refrigerating capacity.

Heretofore, a combination of HFO-1234yf and HFO-1123 has not been foundor indicated in any documents yet, with a view to obtaining a workingfluid which is practically useful comprehensively considering thebalance of the capacity, the efficiency and the temperature glide as analternative to R410A.

HFO-1123 is known to undergo so-called self-decomposition at hightemperature or with an ignition source under high pressure. Therefore,an attempt to suppress self-decomposition reaction by mixing HFO-1123with another component such as vinylidene fluoride to form a mixturehaving a lowered content of HFO-1123 has been reported (Non-PatentDocument 1).

However, Non-Patent Document 1 failed to disclose a composition withwhich a working fluid can be used with durability while maintainingcycle performance of HFO-1123 without any special measures, under thetemperature and pressure conditions under which HFO-1123 is used as theworking fluid, and a method for stably producing it. In a case whereHFO-1123 is used as a working fluid, a composition with which theworking fluid does not undergo self-decomposition and a stableproduction method are necessary.

PRIOR ART DOCUMENTS Patent Documents

-   Patent Document 1: WO2012/157764-   Patent Document 2: JP-A-2012-505296

Non-Patent Document

-   Non-Patent Document 1: Combustion, Explosion, and Shock Waves, Vol.    42, No 2, pp. 140-143, 2006

DISCLOSURE OF INVENTION Technical Problem

The present inventor has confirmed that the critical temperature ofHFO-1123 is 59.2° C. Thus, it was found that as an alternative toconventionally used R410A, HFO-1123 has a low critical temperature andit can substitute working fluids only in a limited range. Further, evenwhen various HFCs disclosed in Patent Document 1 are combined,sufficient coefficient of performance and refrigerating capacity cannotnecessarily be achieved. The object of the present invention is toprovide a working fluid for heat cycle which achieves not only thecritical temperature but also sufficient cycle performance as analternative to R410A simultaneously, a composition for a heat cyclesystem comprising the working fluid, and a heat cycle system employingthe composition.

Further, the object of the present invention is to provide a workingfluid for heat cycle with which practically sufficient cycle performancewill be obtained while suppressing the influence over global warming,and which has high durability without any special measures, acomposition for a heat cycle system comprising the working fluid, and aheat cycle system employing the composition.

Solution to Problem

Under these circumstances, the present inventor has accomplished thepresent invention by intentionally using HFO-1234yf having a lowrefrigerating capacity and further HFC-32 in combination with HFO-1123to obtain a working fluid having a specific composition.

That is, the present invention provides a working fluid for heat cycle,a composition for a heat cycle system and a heat cycle system of thefollowing [1] to [8].

[1] A working fluid for heat cycle, which contains HFO-1123, HFO-1234yfand HFC-32, wherein the proportion of the total amount of HFO-1123,HFO-1234yf and HFC-32 based on the entire amount of the working fluid ishigher than 90 mass % and at most 100 mass %, and based on the totalamount of HFO-1123, HFO-1234yf and HFC-32, the proportion of HFO-1123 isat least 10 mass % and less than 70 mass %, the proportion of HFO-1234yfis at most 50 mass %, and the proportion of HFC-32 is higher than 30mass % and at most 75 mass %.

[2] The working fluid for heat cycle according to [1], wherein theproportion of HFC-32 based on the total amount of HFO-1123, HFO-1234yfand HFC-32 is higher than 30 mass % and at most 44 mass %.

[3] The working fluid for heat cycle according to [1] or [2], whereinbased on the total amount of HFO-1123, HFO-1234yf and HFC-32, theproportion of HFO-1123 is at least mass % and less than 70 mass %, andthe proportion of HFO-1234yf is at most 40 mass %.

[4] The working fluid for heat cycle according to any one of [1] to [3],wherein based on the total amount of HFO-1123, HFO-1234yf and HFC-32,the proportion of HFO-1234yf is at least 5 mass % and at most 40 mass %.

[5] A composition for a heat cycle system, which comprises the workingfluid for heat cycle as defined in any one [1] to [4] and a lubricatingoil.

[6] A heat cycle system, which employs the composition for a heat cyclesystem as defined in [5].

[7] The heat cycle system according to [6], which is a refrigeratingapparatus, an air-conditioning apparatus, a power generation system, aheat transport apparatus or a secondary cooling machine.

[8] The heat cycle system according to [6], which is a roomair-conditioner, a store package air-conditioner, a building packageair-conditioner, a plant package air-conditioner, a gas engine heatpump, a train air-conditioning system, an automobile air-conditioningsystem, a built-in showcase, a separate showcase, an industrial fridgefreezer, an ice making machine or a vending machine.

Advantageous Effects of Invention

The working fluid for heat cycle and the composition for a heat cyclesystem containing the working fluid of the present invention have lessinfluence over global warming and have practically sufficient cycleperformance when used for heat cycle, and are excellent in durability.

The heat cycle system of the present invention, which employs thecomposition for a heat cycle system of the present invention, has lessinfluence over global warming and has practically sufficient cycleperformance, and is excellent in durability.

Further, the working fluid for heat cycle of the present invention hasthe above excellent properties and can replace conventionally usedR410A.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram illustrating a composition range of an embodiment ofa working fluid for heat cycle of the present invention in triangularcoordinates of a composition (mass %) of a mixture of HFO-1123,HFO-1234yf and HFC-32.

FIG. 2 is a graph showing the relation between the composition and thetemperature glide of a mixed fluid of HFO-1123 and HFO-1234yf.

FIG. 3 is a schematic construction view illustrating a refrigeratingcycle system as an example of a heat cycle system of the presentinvention.

FIG. 4 is a diagram illustrating a preferred composition range of anembodiment of a working fluid for heat cycle of the present invention intriangular coordinates of a composition (mass %) of a mixture ofHFO-1123, HFO-1234yf and HFC-32.

FIG. 5 is a diagram illustrating a more preferred composition range ofan embodiment of a working fluid for heat cycle of the present inventionin triangular coordinates of a composition (mass %) of a mixture ofHFO-1123, HFO-1234yf and HFC-32.

FIG. 6 is a cycle diagram illustrating the state change of a workingfluid in a refrigerating cycle system in FIG. 3 on a pressure-enthalpychart.

DESCRIPTION OF EMBODIMENTS

Now, the present invention will be described in detail.

<Working Fluid for Heat Cycle>

The working fluid of the present invention is a working fluid for heatcycle, which contains HFO-1123, HFO-1234yf and HFC-32, wherein theproportion of the total amount of HFO-1123, HFO-1234yf and HFC-32 basedon the entire amount of the working fluid is higher than 90 mass %, andat most 100 mass %, and based on the total amount of HFO-1123,HFO-1234yf and HFC-32, the proportion of HFO-1123 is at least 10 mass %and less than 70 mass %, the proportion of HFO-1234yf is at most 50 mass%, and the proportion of HFC-32 is higher than 30 mass % and at most 75mass %.

As heat cycle, heat cycle by a heat exchanger such as a condenser or anevaporator may be used without any particular restriction.

The working fluid of the present invention, which contains HFO-1123,HFO-1234yf and HFC-32 within the above ranges, is a working fluid in abalanced manner which makes up for disadvantages of the respectivecompounds while making use of properties of the respective compounds.Specifically, it is a working fluid which has practically sufficientcycle performance as an alternative to conventional R410A, has a lowglobal warming potential, and has no self-decomposition property.

Now, the composition of the working fluid according to an embodiment ofthe present invention will be described with reference to FIGS. 1 to 3 .

FIG. 1 illustrates the composition range in a case where the workingfluid for heat cycle of the present invention comprises HFO-1123,HFO-1234yf and HFC-32 and contains no other component, that is, thecomposition range in a case where based on the total amount of HFO-1123,HFO-1234yf and HFC-32, the proportion of the HFO-1123 is at least 10mass % and less than 70 mass %, the proportion of HFO-1234-yf is at most50 mass %, and the proportion of HFC-32 is higher than 30 mass % and atmost 75 mass % (hereinafter sometimes referred to as the compositionrange (S)). FIG. 1 illustrates triangular coordinates indicating thecomposition (mass %) of HFO-1123, HFO-1234yf and HFC-32 by therespective three sides, and a pentangular region surrounded by a heavysolid line corresponds to the composition range (S) of a working fluidaccording to an embodiment of the present invention.

The sides (S1) to (S5) of the pentagon indicating the composition range(S) in FIG. 1 respectively indicate boundaries of the following ranges.In the following formulae, abbreviated names of the respective compoundsindicate the proportions (mass %) of the respective compounds based onthe entire amount of the working fluid, that is, the total amount ofHFO-1123, HFO-1234yf and HFC-32.

-   -   (S1) HFC-32≤75 mass %    -   (S2) 0 mass %<HFO-1234yf    -   (S3) 30 mass %<HFC-32    -   (S4) HFO-1234yf≤50 mass %    -   (S5) 10 mass %≤HFO-1123

Now, the relation between the composition range (S) and the performanceas the working fluid, specifically, the global warming potential, thecycle performance, the temperature glide and the self-decompositionproperty will be described.

(Global Warming Potential (GWP))

In this specification, GWP is a value (100 years) in IntergovernmentalPanel on Climate Change (IPCC), Fourth assessment report (2007), unlessotherwise specified. Further, GWP of a mixture is represented by aweighted average by the composition mass.

GWPs of HFO-1234yf and HFC-32 contained in the working fluid of thepresent invention are 4 and 675, respectively, and the global warmingpotential (100 years) of HFO-1123 is 0.3 as a value measured inaccordance with IPCC Fourth assessment report.

In the composition range (S) shown in FIG. 1 according to an embodimentof the working fluid of the present invention, the composition withhighest GWP is the composition at the upper right angle of the pentagon,that is, the composition comprising HFO-1123:HFO-1234yf:HFC-32 of 10mass %:15 mass %:75 mass %, and GWP with the composition is calculatedas (0.3×10+4×15+675×75)/100=506.9. This is a value of at most ¼ ascompared with GWP of R410A of 2087.5.

GWP of a mixture is a weighted average by the composition mass of eachcomponent as described above. Since GWPs of HFO-1123 and HFO-1234yf arevery low as compared with GWP of HFC-32, GWP of a composition comprisingHFO-1123, HFO-1234yf and HFC-32 greatly depends on the content ofHFC-32.

Accordingly, in view of only GWP of the working fluid, in the triangularcoordinates in FIG. 1 , the closer to the lower side, the lower GWP ofthe composition and the more preferred. However, in the presentinvention, the lower side in the composition range (S) is limited to(S3) 30 mass %<HFC-32 considering the balance of the cycle performance,the temperature glide and the self-decomposition property as describedhereinafter.

The working fluid of the present invention may contain an optionalcomponent other than HFO-1123, HFO-1234yf and HFC-32 in a proportion ofat most 10 mass %. It is preferred that the working fluid does notcontain, as an optional component, a component which excessivelyincreases GWP of the working fluid. GWP of the working fluid of thepresent invention is preferably at most 500, more preferably at most300.

(Cycle Performance)

The cycle performance of the working fluid may be a coefficient ofperformance and a refrigerating capacity.

The coefficient of performance and the refrigerating capacity of each ofHFO-1123, HFO-1234yf and HFC-32 contained in the working fluid of thepresent invention, measured by the after-mentioned Examples, as relativevalues based on R410A (1.000) are shown in Table 1.

As evident from Table 1, although HFO-1123 has an excellentrefrigerating capacity as a working fluid, it may not be sufficient inview of the coefficient of performance as compared with other HFOs.Further, when HFO-1123 is used alone, from the viewpoint of the criticaltemperature, sufficient refrigerating cycle performance may not beexpected in some cases for an application in which R410A has been used.

HFO-1234yf is a HFO having the refrigerating capacity and thecoefficient of performance as a working fluid in a balanced manner.Although the critical temperature (94.7° C.) of HFO-1234yf is high ascompared with HFO-1123, its capacity when used alone is insufficient ascompared with R410A.

Further, although HFC-32 is excellent in the coefficient of performanceand the refrigerating capacity, its GWP is high as compared withHFO-1123 and HFO-1234yf. However, GWP of HFC-32 is remarkably low ascompared with R410A.

TABLE 1 Working fluid Relative performance composition (relative toR410A) [mass %] Relative Relative HFO- HFO- coefficient of refrigerating1123 1234yf HFC-32 performance capacity GWP Ex. 33 100  0  0 0.921 1.146  0.3 Ex. 34  0 100  0 1.046 0.422   4.0 Ex. 35  0  0 100 1.009 1.109 675.0 Ex. 57 Working fluid 1.000 1.000 2087.5 (R410A) comprisingHFC-125 and HFC-32 in a mass ratio of 1:1

Here, in the composition range (S) in FIG. 1 indicating the compositionrange of HFO-1123, HFO-1234yf and HFC-32 in the working fluid of thepresent invention, the composition with a coefficient of performance asa relative performance relative to R410A (hereinafter sometimes referredto as “relative coefficient of performance”) being at least 1.000 is acomposition at the side (S5) and in the vicinity thereof. Further, thecomposition with the minimum relative coefficient of performance is acomposition at the lower left angle in the pentagon indicating thecomposition range (S).

Further, in the composition range (S) in FIG. 1 , the composition with arefrigerating capacity as a relative performance relative to R410A(hereinafter sometimes referred to as “relative refrigerating capacity”)being at least 1.000 is a composition at the side (S2) and in thevicinity thereof. Further, the composition with the minimum relativecoefficient of performance is a composition at the rightmost angle inthe pentagon indicating the composition range (S). The relativerefrigerating capacity can be considered to greatly depend on thecontent of HFO-1234yf.

When the relative coefficient of performance and the relativerefrigerating capacity are certain values or higher, and a product ofthe relative coefficient of performance and the relative refrigeratingcapacity as an index is a certain value or higher, such a working fluidcan be considered to be in good balance of the cycle performance.

The working fluid preferably has a relative coefficient of performanceof at least 0.958 and a relative refrigerating capacity of at least0.820, more preferably a relative coefficient of performance of at least0.980 and a relative refrigerating capacity of at least 0.950,particularly preferably a relative coefficient of performance of atleast 1.000 and a relative refrigerating capacity of at least 1.000.From the viewpoint of the relative coefficient of performance, (S2) ispreferably 5 mass %≤HFO-1234yf, more preferably 8 mass %≤HFO-1234yf.Further, with respect to the relation between the relative coefficientof performance and the relative refrigerating capacity, in a case whereboth the relative coefficient of performance and the relativerefrigerating capacity are lower than 1.000, their product is preferablyat least 0.950.

The working fluid of the present invention may contain an optionalcomponent other than HFO-1123, HFO-1234yf and HFC-32 in a proportion ofat most 10 mass %. It is preferred that the working fluid of the presentinvention does not contain, as an optional component, a component whichexcessively decreases the relative coefficient of performance and therelative refrigerating capacity of the working fluid.

(Temperature Glide)

In a case where a mixture is used as the working fluid, it is preferablyan azeotropic mixture or a pseudoazeotropic mixture such as R410A. Anon-azeotropic mixture has a problem such that when it is put into arefrigerator or an air-conditioning apparatus from a pressure container,it undergoes a composition change. Further, if a refrigerant leaks outfrom a refrigerator or an air-conditioning apparatus, the refrigerantcomposition in the refrigerator or the air-conditioning apparatus isvery likely to change, and a recovery to an initial refrigerantcomposition is hardly possible. Such problems can be avoided with anazeotropic or pseudoazeotropic mixture.

As an index to the above properties of a mixture as the working fluid,the following “temperature glide” is commonly employed. The temperatureglide is defined as properties such that the initiation temperature andthe completion temperature of evaporation in an evaporator or ofcondensation in a condenser, for example, as the heat exchanger, differfrom each other. The temperature glide of an azeotropic mixture fluid is0, and the temperature glide of a pseudoazeotropic mixture fluid, suchas R410A, is extremely close to 0.

If the temperature glide is large, for example, the inlet temperature ofan evaporator tends to be low, and frosting is likely to occur. Further,in a heat cycle system, the heat exchange efficiency is to be improvedby making the working fluid and the heat source fluid such as water orthe air flowing in heat exchangers flow in counter-current flow. Sincethe temperature difference of the heat source fluid is small in a stableoperation state, it is difficult to obtain a heat cycle system with agood energy efficiency with a non-azeotropic mixture fluid with a largetemperature glide. Accordingly, a non-azeotropic mixture fluid with anappropriate temperature glide is desired.

HFO-1123 and HFO-1234yf in the working fluid of the present inventionare not in an azeotropic state. The relation between the temperatureglide and the composition of a mixed fluid of HFO-1123 and HFO-1234yfmeasured by the method disclosed in after-mentioned Examples is shown inFIG. 2 . Further, it was confirmed by the present inventor that HFO-1123and HFC-32 are in the form of a pseudoazeotropic mixture close to anazeotropic mixture within a composition range of from 99:1 to 1:99 bymass ratio.

From the above relation, a mixture of HFO-1123, HFO-1234yf and HFC-32 isconsidered to have a temperature glide. Further, from the relationbetween HFO-1123 and HFO-1234yf and the relation between HFO-1123 andHFC-32, in the composition range (S) in FIG. 1 indicating thecomposition range of HFO-1123, HFO-1234yf and HFC-32 in the workingfluid of the present invention, the following can be confirmed.

In the composition range (S) in FIG. 1 , the closer to the side (S2),that is, the lower the content of HFO-1234yf, the closer to 0 thetemperature glide is. Further, the temperature glide is smallest with acomposition at the lower limit of (S2), that is, at the lower left anglein the pentagon indicating the composition range (S). On the other hand,the higher the content of HFO-1234yf, that is, the closer to the side(S4), the larger the temperature glide. Further, the temperature glideis largest with a composition at the lower limit of (S4), that is, atthe lower right angle in the pentagon indicating the composition range(S).

Further, in Table 2, the composition, the temperature glide and GWP of aworking fluid having a HFO-1234yf content of 50 mass % among workingfluids prepared in Examples of the present invention and ComparativeExamples, are shown. Further, for comparison, the temperature glide andGWP of a working fluid comprising HFO-1123 and HFO-1234yf in a massratio of 1:1 and R410A are shown.

TABLE 2 Working fluid composition [mass %] Temperature HFO-1123HFO-1234yf HFC-32 glide [° C.] GWP Ex. 5 10 50 40 5.8 272.0 Ex. 30 20 5030 6.6 204.6 Ex. 27 30 50 20 7.1 137.1 Ex. 19 40 50 10 7.3 69.6 Ex. 3650 50 0 7.2 2.2 Ex. 57 Working fluid comprising 0.2 2087.5 (R410A)HFC-125 and HFC-32 in a mass ratio of 1:1

As evident from Table 2, even at the same content of HFO-1234yf being 50mass %, the temperature glide is small when the content of HFC-32 ishigh, as compared with HFO-1123. Accordingly, as the working fluid ofthe present invention, for example, the composition range (S) which is acomposition with low GWP and small temperature glide is selected in thetriangular coordinates in FIG. 1 .

In the composition range (S) in a case where the working fluid of thepresent invention comprises HFO-1123, HFO-1234yf and HFC-32, withreference to FIG. 1 and Table 2, the temperature glide is less than 6.6°C., which is a practically preferred range, as an alternative to R410A.The temperature glide of the working fluid comprising HFO-1123,HFO-1234yf and HFC-32 is more preferably less than 5.8° C.

Further, the working fluid of the present invention may contain anoptional component other than HFO-1123, HFO-1234yf and HFC-32 in aproportion of at most mass %. It is preferred that the working fluid ofthe present invention does not contain, as an optional component, acomponent which excessively increases the temperature glide of theworking fluid. The temperature glide of the working fluid of the presentinvention is preferably at most 6° C., more preferably at most 5° C.

The influence in a heat cycle system when the working fluid of thepresent invention has a temperature glide will be described withreference to a case where the working fluid is used for a heat cyclesystem shown in FIG. 3 . FIG. 3 is a schematic construction viewillustrating a refrigerating cycle system as an example of a heat cyclesystem of the present invention.

A refrigerating cycle system 10 comprises a compressor 11 to compress aworking fluid (vapor), a condenser 12 to cool and liquefy the workingfluid vapor discharged from the compressor 11, an expansion valve 13 tolet the working fluid (liquid) discharged from the condenser 12 expand,and an evaporator 14 to heat and vaporize the working fluid in a liquidstate discharged from the expansion valve 13.

In the refrigerating cycle system 10, the temperature of the workingfluid increases from an inlet toward an outlet of the evaporator 14 atthe time of evaporation, and on the contrary, the temperature decreasesfrom an inlet toward an outlet of the condenser 12 at the time ofcondensation. In the refrigerating cycle system 10, such is achieved byheat exchange between the working fluid and a heat source fluid such aswater or the air flowing to face the working fluid in the evaporator 14or the condenser 12. The heat source fluid is represented by E→E′ in theevaporator 14 and by F→F′ in the condenser 12 in the refrigerating cyclesystem 10.

Here, when a single fluid or an azeotropic mixture fluid is used, sincethere is no temperature glide, the temperature difference between theoutlet temperature and the inlet temperature of the evaporator 14 issubstantially constant, however, when a non-azeotropic mixture fluid isused, the temperature difference will not be constant. For example, in acase where the working fluid is to be evaporated at 0° C. in theevaporator 14, the inlet temperature is lower than 0° C., and frostingmay occur in the evaporator 14. Particularly, the larger the temperatureglide, the lower the inlet temperature and the more frosting is likelyto occur.

Further, in a case where a non-azeotropic mixture fluid with a largetemperature glide is used for the refrigerating cycle system 10, sincethe compositions of the gaseous phase and the liquid phase aresignificantly different from each other, if the non-azeotropic mixturefluid circulating in the system 10 leaks out, the composition of thenon-azeotropic mixture fluid circulating in the system 10 maysignificantly change as between before and after the leakage.

Further, for example, as shown in the refrigerating cycle system 10,usually in the heat cycle system, the heat exchange efficiency is to beimproved by making the working fluid and the heat source fluid such aswater or the air flowing in heat exchangers such as the evaporator 14and the condenser 12 flow in counter-current flow. Here, since thetemperature difference of the heat source fluid is small usually in along-term stable operation state except for at the time of start-up, itis difficult to obtain a heat cycle system with a good energy efficiencywith a non-azeotropic mixture fluid with a large temperature glide.Accordingly, a non-azeotropic mixture fluid with an appropriatetemperature glide is desired.

As described above, the composition range of the combination ofHFO-1123, HFO-1234yf and HFC-32 in the working fluid of the presentinvention is a range within which the working fluid has a practicaltemperature glide.

(Self-Decomposition Property)

HFO-1123 contained in the working fluid of the present invention isknown to have self-decomposition property. However, under thetemperature and pressure conditions under which HFO-1123 is used as aworking fluid, a composition with which the working fluid can be usedwith durability while maintaining refrigerating cycle performance ofHFO-1123 has not been known. Accordingly, the present inventor hasconfirmed that self-decomposition can be suppressed under thetemperature and pressure conditions under which a composition containingHFO-1123 is used as a working fluid, when the content of HFO-1123 basedon the entire amount of the composition is at most 70 mol %.

<Evaluation of Self-Decomposition Property of HFO-1123>

The self-decomposition property was evaluated in equipment in accordancewith method A recommended as equipment for measurement of the combustionrange of a gas mixture containing halogen, by individual notificationsin High Pressure Gas Safety Act.

Specifically, a mixed fluid of HFO-1123 and HFO-1234yf, HFO-1123 andHFC-32, or HFO-1123, HFO-1234yf and HFC-32, in various proportions, isenclosed in a spherical pressure resistant reactor having an internalcapacity of 650 cm³ and having a predetermined temperature controlledfrom the outside to a predetermined pressure, and then a platinum wiredisposed in the interior was fused to apply an energy of about J.Whether the self-decomposition reaction occurred or not was confirmed bymeasuring the temperature and pressure changes in the pressure resistantreactor after the application. A case where a pressure increase and atemperature increase were confirmed was evaluated as self-decompositionreaction occurred. The results are shown in Table 3 with respect tomixed fluids of HFO-1123 and HFO-1234yf, in Table 4 with respect tomixed fluids of HFO-1123 and HFC-32, and in Table 5 with respect tomixed fluids of HFO-1123, HFO-1234yf and HFC-32. The pressure in Tables3 to 5 is the gage pressure.

TABLE 3 HFO-1123/ Pressure Temperature HFO-1234yf [MPaG] [° C.] Self-[mass %/ [mol %/ Before After Before After decomposition mass %] mol %]ignition ignition ignition ignition reaction 52/48 60/40 0.98 0.98 250250.2 Nil 63/37 70/30 0.98 0.98 250 250.2 Nil 74/26 80/20 0.98 4.00 250291.6 Occurred 87/13 90/10 0.98 4.80 250 291.1 Occurred

TABLE 4 HFO-1123/ Pressure Temperature HFC-32 [MPaG] [° C.] Self- [mass%/ [mol %/ Before After Before After decomposition mass %] mol %]ignition ignition ignition ignition reaction 70/30 60/40 0.98 0.98 250250.5 Nil 80/20 72/28 0.98 0.98 250 250.4 Nil 85/15 78/22 0.98 4.60 250290.0 Occurred

TABLE 5 HFO-1123/HFO- 1234yf/HFC-32 Pressure Temperature [mass %/ [mol%/ [MPaG] [º C.] Self- mass %/ mol %/ Before After Before Afterdecomposition mass %] mol %] ignition ignition ignition ignitionreaction 70/10/20 64/7/29 0.98 0.98 250 250.5 Nil 70/20/10 70/14/16 0.980.98 250 250.5 Nil 80/10/10 78/7/15 0.98 4.00 250 289.5 Occurred

The composition range (S) of the working fluid according to anembodiment of the present invention does not contain a composition rangewith self-decomposition property thus confirmed. That is, when theworking fluid of the present invention is a working fluid within theabove composition range (S) consisting solely of HFO-1123, HFO-1234yfand HFC-32, the content of HFO-1123 based on the entire amount of theworking fluid is at most 70 mol %.

The working fluid of the present invention may contain an optionalcomponent other than HFO-1123, HFO-1234yf and HFC-32 in a proportion ofat most 10 mass %. As the optional component, a compound having noself-decomposition property is preferably selected.

The working fluid in the composition range (S) is a working fluid havingrespective characteristics of HFO-1123, HFO-1234yf and HFC-32 in abalanced manner, and having defects of the respective componentssuppressed. That is, the working fluid in the composition range (S) is aworking fluid which has a low GWP, has durability secured, and has asmall temperature glide and has a certain performance and efficiencywhen used for heat cycle, and thus with such a working fluid, favorablecycle performance will be obtained.

In a case where the working fluid of the present invention is consistssolely of three compounds of HFO-1123, HFO-1234yf and HFC-32, apreferred composition may be a composition such that based on the totalamount of HFO-1123, HFO-1234yf and HFC-32, the proportion of HFO-1123 isat least 10 mass % and less than 70 mass %, the proportion of HFO-1234yfis at most 50 mass %, and the proportion of HFC-32 is higher than 30mass % and at most 44 mass %. This composition range will be describedbelow as the composition range (P).

The composition range (P) in a case where the working fluid for heatcycle of the present invention comprises HFO-1123, HFO-1234yf and HFC-32is shown in triangular coordinates in FIG. 4 . That is, FIG. 4illustrates triangular coordinates indicating the composition (mass %)of HFO-1123, HFO-1234yf and HFC-32 by the respective three sides, and aband-form pentangular region surrounded by a heavy solid linesubstantially at the center portion of the triangular coordinates,corresponds to the composition range (P) of a preferred working fluid ofthe present invention.

The sides (P1) to (P5) of the pentagon indicating the composition range(P) in FIG. 4 respectively indicate boundaries of the following ranges.In the following formulae, abbreviated names of the respective compoundsindicate the proportions (mass %) of the respective compounds based onthe entire amount of the working fluid, that is, the total amount ofHFO-1123, HFO-1234yf and HFC-32, in the same manner as the above (S1) to(S5).

-   -   (P1) HFC-32≤44 mass %    -   (P2) 0 mass %<HFO-1234yf    -   (P3) 30 mass %<HFC-32    -   (P4) HFO-1234yf≤50 mass %    -   (P5) 10 mass %≤HFO-1123

Of the above (P1) to (P5) in the composition range (P), (P2) to (P5) arethe same as (S2) to (S5) in the composition range (S). In thecomposition range (P), the upper limit content of HFC-32 is lower andthe upper limit of GWP is lower than in the composition range (S). Inthe composition range (P) shown in FIG. 4 , the composition with highestGWP is the composition at the upper right angle of the pentagon, thatis, the composition comprising HFO-1123:HFO-1234yf:HFC-32 of 10 mass%:46 mass %:44 mass %, and GWP with the composition is calculated as(0.3×10+4×46+675×44)/100=298.9. In view of a high relative coefficientof performance, (P2) is preferably 5 mass %≤HFO-1234yf, more preferably8 mass %≤HFO-1234yf.

Further, in a case where the working fluid of the present invention isconstituted of three compounds of HFO-1123, HFO-1234yf and HFC-32,another preferred composition may be a composition in which based on thetotal amount of HFO-1123, HFO-1234yf and HFC-32, the proportion ofHFO-1123 is at least 20 mass % and less than 70 mass %, the proportionof HFO-1234yf is at most 40 mass %, and the proportion of HFC-32 ishigher than 30 mass % and at most 75 mass %. More preferred is such acomposition wherein the upper limit of the proportion of HFC-32 is 44mass %. Further preferred is such a composition wherein the lower limitof the proportion of HFO-1234yf is 5 mass %. The further preferredcomposition range will be described below as the composition range (M).

The composition range (M) in a case where the working fluid for heatcycle of the present invention comprises HFO-1123, HFO-1234yf and HFC-32is shown in triangular coordinates in FIG. 5 . That is, FIG. 5illustrates triangular coordinates indicating the composition (mass %)of HFO-1123, HFO-1234yf and HFC-32 by the respective three sides, and apentangular region surrounded by a heavy solid line at the left sidesubstantially at the center portion of the triangular coordinates,corresponds to the composition range (M) of the further preferredworking fluid of the present invention.

The sides (M1) to (M5) of the pentagon indicating the composition range(M) in FIG. 5 respectively indicate boundaries of the following ranges.In the following formulae, abbreviated names of the respective compoundsindicate the proportions (mass %) of the respective compounds based onthe entire amount of the working fluid, that is, the total amount ofHFO-1123, HFO-1234yf and HFC-32, in the same manner as the above (S1) to(S5).

-   -   (M1) HFC-32≤44 mass %    -   (M2) 5 mass %≤HFO-1234yf    -   (M3) 30 mass %<HFC-32    -   (M4) HFO-1234yf≤40 mass %    -   (M5) 20 mass %≤HFO-1123

Of the above (M1) to (M5) in the composition range (M), (M1) and (M3)are the same as (P1) and (P3) in the composition range (P). In thecomposition range (M), as compared with the composition range (P), therange of the HFO-1234yf content is narrowed from “higher than 0 mass %and at most 50 mass %” to “at least 5 mass % and at most 40 mass %”, andthe lower limit of the HFO-1123 content was increased from 10 mass % to20 mass %. Within such a range, the upper limit of the temperature glideis lowered, and the lower limit of the product of the relativecoefficient of performance and the relative refrigerating capacity isincreased. In view of a high relative coefficient of performance, (M2)is more preferably 8 mass %≤HFO-1234yf. Further, in view of a highrelative refrigerating capacity, (M4) is more preferably HFO-1234yf≤35mass %.

The working fluid in the composition range (M) is a working fluid havingrespective characteristics of HFO-1123, HFO-1234yf and HFC-32 in abalanced manner, and having defects of the respective componentssuppressed. That is, the working fluid in the composition range (M) is aworking fluid of which the upper limit of GWP is suppressed to be so lowas at most 300, which has durability secured, and which has a smalltemperature glide of less than 5.8 and has a relative coefficient ofperformance and a relative refrigerating capacity close to 1, when usedfor heat cycle, and thus with such a working fluid, favorable cycleperformance will be obtained.

[Optional Component]

The working fluid of the present invention may optionally contain acompound commonly used for a working fluid, in a proportion of at most10 mass % based on the entire amount of the working fluid, in additionto HFO-1123, HFO-1234yf and HFC-32, within a range not to impair effectsof the present invention. Even when the working fluid of the presentinvention contains an optional compound in addition to HFO-1123,HFO-1234yf and HFC-32 (which will be referred to as an optionalcomponent), the temperature glide of the working fluid will not be 0 andthe working fluid has a considerable temperature glide. The temperatureglide of the working fluid of the present invention varies dependingupon the mixture ratio of HFO-1123, HFO-1234yf and HFO-1234yf and theoptional component contained as the case requires.

The optional component includes a HFC other than HFC-32 or a HFO (a HFChaving a carbon-carbon double bond) other than HFO-1123 and HFO-1234yf.

(HFC Other than HFC-32)

As the HFC other than HFC-32 which the working fluid of the presentinvention may optionally contain, for example, a HFC having an effect todecrease the temperature glide, to improve the capacity or to furtherincrease the efficiency, when used in combination with HFO-1123,HFO-1234yf and HFC-32 for heat cycle, is used. When the working fluid ofthe present invention contains such a HFC other than HFC-32, morefavorable cycle performance will be obtained.

A HFC is known to have a high GWP as compared with HFO-1123 andHFO-1234yf. Accordingly, a HFC as the optional component is selectedwith a view to adjusting the GWP within an acceptable range, in additionto improving cycle performance as the working fluid.

A HFC as an optional component, which has less influence over the ozonelayer and which has less influence over global warming, is specificallypreferably a C₁₋₅ HFC. The HFC other than HFC-32 may be linear, branchedor cyclic.

The HFC other than HFC-32 may, for example, be difluoroethane,trifluoroethane, tetrafluoroethane, pentafluoroethane (HFC-125),pentafluoropropane, hexafluoropropane, heptafluoropropane,pentafluorobutane or heptafluorocyclopentane.

Particularly, in view of less influence over the ozone layer andexcellent refrigerating cycle performance, the HFC other than HFC-32 ispreferably 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane(HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134),1,1,1,2-tetrafluoroethane (HFC-134a) or HFC-125, more preferablyHFC-134a or HFC-125.

However, HFC-134a and HFC-125 have very high global warming potentialsof 1,430 and 3,500, respectively. When they are used as optionalcomponents of the working fluid, they are incorporated so that GWP ofthe working fluid will not exceed the acceptable range.

The HFC other than HFC-32 may be used alone or in combination of two ormore.

(HFO Other than HFO-1123 and HFO-1234yf)

The HFO other than HFO-1123 and HFO-1234yf may, for example, be1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf),1,1,2-trifluoropropene (HFO-1243yc), trans-1,2,3,3,3-pentafluoropropene(HFO-1225ye(E)), cis-1,2,3,3,3-pentafluoropropene (HFO-1225ye(Z)),trans-1,3,3,3-tetrafluoropropene (HFO-1234ze(E)),cis-1,3,3,3-tetrafluoropropene (HFO-1234ze(Z)) or 3,3,3-trifluoropropene(HFO-1243zf).

Particularly, the HFO other than HFO-1123 and HFO-1234yf is, in view ofa high critical temperature and excellent durability and coefficient ofperformance, preferably HFO-1234ze(E) or HFO-1234ze(Z), more preferablyHFO-1234ze(E).

The HFO other than HFO-1123 and HFO-1234yf may be used alone or incombination of two or more.

In a case where the working fluid of the present invention contains theoptional component, its content is at most 10 mass %, preferably at most8 mass %.

The content of the optional component is properly adjusted within theabove range, with a view to lowering the temperature glide, improvingthe capacity or further increasing the efficiency, while durability issecured, and further considering the global warming potential, when theworking fluid of the present invention is used for heat cycle.

The composition range by HFO-1123, HFO-1234yf and HFC-32 in the workingfluid of the present invention is a composition range in which thebalance of the durability, the temperature glide, the refrigeratingcapacity, the coefficient of performance and the global warmingpotential is adjusted by the three components alone, and accordingly animprovement of any of such characteristics without disturbing thebalance by addition of an optional component may be difficult in somecases. Particularly when the working fluid is in the above preferredcomposition range, such improvement is difficult. Accordingly, theworking fluid of the present invention preferably contains no othercomponent than HFO-1123, HFO-1234yf and HFC-32 except for the followingother optional component incorporated for the purpose of improving thesolubility in a lubricating oil or imparting flame retardancy.

(Other Optional Component)

The working fluid of the present invention may contain, other than theabove optional component, carbon dioxide, a hydrocarbon, achlorofluoroolefin (CFO), a hydrochlorofluoroolefin (HCFO), etc. Suchanother optional component is preferably a component which has lessinfluence over the ozone layer and which has less influence over globalwarming.

The hydrocarbon may, for example, be propane, propylene, cyclopropane,butane, isobutane, pentane or isopentane.

The hydrocarbon may be used alone or in combination of two or more.

In a case where the working fluid of the present invention contains ahydrocarbon, its content is at most 10 mass %, preferably from 1 to 5mass %, more preferably from 3 to 5 mass % per 100 mass % of the workingfluid. When the content of the hydrocarbon is at least the lower limit,the solubility of a mineral lubricating oil in the working fluid will befavorable.

The CFO may, for example, be chlorofluoropropene orchlorofluoroethylene. With a view to suppressing flammability of theworking fluid without significantly decreasing the cycle performance ofthe working fluid of the present invention, the CFO is preferably1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya),1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb) or1,2-dichloro-1,2-difluoroethylene (CFO-1112).

The CFO may be used alone or in combination of two or more.

When the working fluid of the present invention contains the CFO, itscontent is at most 10 mass %, preferably from 1 to 8 mass %, morepreferably from 2 to 5 mass % per 100 mass % of the working fluid. Whenthe content of the CFO is at least the lower limit, the flammability ofthe working fluid tends to be suppressed. When the content of the CFO isat most the upper limit, favorable cycle performance is likely to beobtained.

The HCFO may, for example, be hydrochlorofluoropropene orhydrochlorofluoroethylene. With a view to suppressing the flammabilityof the working fluid without significantly decreasing the cycleperformance of the working fluid of the present invention, the HCFO ispreferably 1-chloro-2,3,3,3-tetrafluoropropene (HCF0-1224yd) or1-chloro-1,2-difluoroethylene (HCFO-1122).

The HCFO may be used alone or in combination of two or more.

In a case where the working fluid of the present invention contains theHCFO, the content of the HCFO per 100 mass % of the working fluid of thepresent invention is at most 1 mass %, preferably from 1 to 8 mass %,more preferably from 2 to 5 mass %. When the content of the HCFO is atleast the lower limit, the flammability of the working fluid tends to besuppressed. When the content of the HCFO is at most the upper limit,favorable cycle performance is likely to be obtained.

When the working fluid of the present invention contains the aboveoptional component, the total content of such optional components in theworking fluid is at most 10 mass %, preferably at most 8 mass %, morepreferably at most 5 mass % per 100 mass % of the working fluid.

The working fluid of the present invention is a working fluid obtainedby mixing HFO-1123 which is excellent in the performance as the workingfluid and HFO-1234yf which has the capacity and the efficiency as theworking fluid in a balanced manner, which are both HFOs having lessinfluence over global warming, and HFC-32 which has a relatively highbut remarkably low GWP than R410A which is excellent in the coefficientof performance and the refrigerating capacity, and which forms anazeotropic or pseudoazeotropic composition with HFO-1123, in combinationin such a proportion as to improve the cycle performance as comparedwith a case where they are respectively used alone, considering thetemperature glide in a mixed fluid of the three, and the working fluidof the present invention has practically sufficient cycle performancewhile suppressing the influence over durability and global warming.

[Application to Heat Cycle System] <Composition for Heat Cycle System>

The working fluid of the present invention may be used, in applicationto a heat cycle system, as the composition for a heat cycle system ofthe present invention usually as mixed with a lubricating oil. Thecomposition for a heat cycle system of the present invention comprisingthe working fluid of the present invention and a lubricating oil mayfurther contain known additives such as a stabilizer and a leakdetecting substance.

(Lubricating Oil)

As a lubricating oil, a known lubricating oil which has been used forthe composition for a heat cycle system together with a working fluidcomprising a halogenated hydrocarbon may be used without any particularrestrictions. The lubricating oil may, for example, be specifically anoxygen-containing synthetic oil (such as an ester lubricating oil or anether lubricating oil), a fluorinated lubricating oil, a minerallubricating oil or a hydrocarbon synthetic oil.

The ester lubricating oil may, for example, be a dibasic acid ester oil,a polyol ester oil, a complex ester oil or a polyol carbonate oil.

The dibasic acid ester oil is preferably an ester of a C₅₋₁₀ dibasicacid (such as glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid or sebacic acid) with a C₁₋₁₅ monohydric alcohol which islinear or has a branched alkyl group (such as methanol, ethanol,propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol,decanol, undecanol, dodecanol, tridecanol, tetradecanol orpentadecanol). Specifically, ditridecyl glutarate, di(2-ethylhexyl)adipate, diisodecyl adipate, ditridecyl adipate or di(3-ethylhexyl)sebacate may, for example, be mentioned.

The polyol ester oil is preferably an ester of a diol (such as ethyleneglycol, 1,3-propanediol, propylene glycol, 1,4-butanediol,1,2-butandiol, 1,5-pentadiol, neopentyl glycol, 1,7-heptanediol or1,12-dodecanediol) or a polyol having from 3 to 20 hydroxy groups (suchas trimethylolethane, trimethylolpropane, trimethylolbutane,pentaerythritol, glycerol, sorbitol, sorbitan or sorbitol/glycerincondensate) with a C₆₋₂₀ fatty acid (such as a linear or branched fattyacid such as hexanoic acid, heptanoic acid, octanoic acid, nonanoicacid, decanoic acid, undecanoic acid, dodecanoic acid, eicosanoic acidor oleic acid, or a so-called neo acid having a quaternary a carbonatom).

The polyol ester oil may have a free hydroxy group.

The polyol ester oil is preferably an ester (such as trimethylolpropanetripelargonate, pentaerythritol 2-ethylhexanoate or pentaerythritoltetrapelargonate) of a hindered alcohol (such as neopentyl glycol,trimethylolethane, trimethylolpropane, trimethylolbutane orpentaerythritol).

The complex ester oil is an ester of a fatty acid and a dibasic acid,with a monohydric alcohol and a polyol. The fatty acid, the dibasicacid, the monohydric alcohol and the polyol may be as defined above.

The polyol carbonate oil is an ester of carbonic acid with a polyol.

The polyol may be the above-described diol or the above-describedpolyol. Further, the polyol carbonate oil may be a ring-opening polymerof a cyclic alkylene carbonate.

The ether lubricating oil may be a polyvinyl ether oil or apolyoxyalkylene oil.

The polyvinyl ether oil may be one obtained by polymerizing a vinylether monomer such as an alkyl vinyl ether, or a copolymer obtained bycopolymerizing a vinyl ether monomer and a hydrocarbon monomer having anolefinic double bond.

The vinyl ether monomer may be used alone or in combination of two ormore.

The hydrocarbon monomer having an olefinic double bond may, for example,be ethylene, propylene, various forms of butene, various forms ofpentene, various forms of hexene, various forms of heptene, variousforms of octene, diisobutylene, triisobutylene, styrene, α-methylstyreneor alkyl-substituted styrene. The hydrocarbon monomer having an olefinicdouble bond may be used alone or in combination of two or more.

The polyvinyl ether copolymer may be either of a block copolymer and arandom copolymer. The polyvinyl ether oil may be used alone or incombination of two or more.

The polyoxyalkylene oil may, for example, be a polyoxyalkylene monool, apolyoxyalkylene polyol, an alkyl ether of a polyoxyalkylene monool or apolyoxyalkylene polyol, or an ester of a polyoxyalkylene monool or apolyoxyalkylene polyol.

The polyoxyalkylene monool or the polyoxyalkylene polyol may be oneobtained by e.g. a method of subjecting a C₂₋₄ alkylene oxide (such asethylene oxide or propylene oxide) to ring-opening additionpolymerization to an initiator such as water or a hydroxygroup-containing compound in the presence of a catalyst such as analkali hydroxide. Further, one molecule of the polyoxyalkylene chain maycontain single oxyalkylene units or two or more types of oxyalkyleneunits. It is preferred that at least oxypropylene units are contained inone molecule.

The initiator to be used for the reaction may, for example, be water, amonohydric alcohol such as methanol or butanol, or a polyhydric alcoholsuch as ethylene glycol, propylene glycol, pentaerythritol or glycerol.

The polyoxyalkylene oil is preferably an alkyl ether or an ester of apolyoxyalkylene monool or polyoxyalkylene polyol. Further, thepolyoxyalkylene polyol is preferably a polyoxyalkylene glycol.Particularly preferred is an alkyl ether of a polyoxyalkylene glycolhaving the terminal hydroxy group of the polyoxyalkylene glycol cappedwith an alkyl group such as a methyl group, which is called a polyglycoloil.

The fluorinated lubricating oil may, for example, be a compound havinghydrogen atoms of a synthetic oil (such as the after-mentioned mineraloil, poly-α-olefin, alkylbenzene or alkylnaphthalene) substituted byfluorine atoms, a perfluoropolyether oil or a fluorinated silicone oil.

The mineral lubricating oil may, for example, be a naphthene mineral oilor a paraffin mineral oil obtained by purifying a lubricating oilfraction obtained by atmospheric distillation or vacuum distillation ofcrude oil by a purification treatment (such as solvent deasphalting,solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing,hydrotreating or clay treatment) optionally in combination.

The hydrocarbon synthetic oil may, for example, be a poly-α-olefin, analkylbenzene or an alkylnaphthalene.

The lubricating oil may be used alone or in combination of two or more.

The lubricating oil is preferably at least one member selected from apolyol ester oil, a polyvinyl ether oil and a polyglycol oil in view ofcompatibility with the working fluid.

The amount of the lubricating oil is not limited within a range not toremarkably decrease the effects of the present invention, and ispreferably from 10 to 100 parts by mass, more preferably from 20 to 50parts by mass, per 100 parts by mass of the working fluid.

(Stabilizer)

The stabilizer is a component which improves the stability of theworking fluid against heat and oxidation. As the stabilizer, a knownstabilizer which has been used for a heat cycle system together with aworking fluid comprising a halogenated hydrocarbon, for example, anoxidation resistance-improving agent, a heat resistance-improving agentor a metal deactivator, may be used without any particular restrictions.

The oxidation resistance-improving agent and the heatresistance-improving agent may, for example, beN,N′-diphenylphenylenediamine, p-octyldiphenylamine,p,p′-dioctyldiphenylamine, N-phenyl-1-naphthyamine,N-phenyl-2-naphthylamine, N-(p-dodecyl)phenyl-2-naphthylamine,di-1-naphthylamine, di-2-naphthylamine, N-alkylphenothiazine,6-(t-butyl)phenol, 2,6-di-(t-butyl)phenol,4-methyl-2,6-di-(t-butyl)phenol or4,4′-methylenebis(2,6-di-t-butylphenol). Each of the oxidationresistance-improving agent and the heat resistance-improving agent maybe used alone or in combination of two or more.

The metal deactivator may, for example, be imidazole, benzimidazole,2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole,salicylidene-propylenediamine, pyrazole, benzotriazole, tritriazole,2-methylbenzamidazole, 3,5-dimethylpyrazole, methylenebis-benzotriazole,an organic acid or an ester thereof, a primary, secondary or tertiaryaliphatic amine, an amine salt of an organic acid or inorganic acid, aheterocyclic nitrogen-containing compound, an amine salt of an alkylphosphate, or a derivative thereof.

The amount of the stabilizer is not limited within a range not toremarkably decrease the effects of the present invention, and ispreferably at most 5 parts by mass, more preferably at most 1 part bymass per 100 parts by mass of the working fluid.

(Leak Detecting Substance)

The leak detecting substance may, for example, be an ultravioletfluorescent dye, an odor gas or an odor masking agent.

The ultraviolet fluorescent dye may be known ultraviolet fluorescentdyes which have been used for a heat cycle system together with aworking fluid comprising a halogenated hydrocarbon, such as dyes asdisclosed in e.g. U.S. Pat. No. 4,249,412, JP-A-10-502737,JP-A-2007-511645, JP-A-2008-500437 and JP-A-2008-531836.

The odor masking agent may be known perfumes which have been used for aheat cycle system together with a working fluid comprising a halogenatedhydrocarbon, such as perfumes as disclosed in e.g. JP-A-2008-500437 andJP-A-2008-531836.

In a case where the leak detecting substance is used, a solubilizingagent which improves the solubility of the leak detecting substance inthe working fluid may be used.

The solubilizing agent may be ones as disclosed in e.g.JP-A-2007-511645, JP-A-2008-500437 and JP-A-2008-531836.

The amount of the leak detecting substance is not particularly limitedwithin a range not to remarkably decrease the effects of the presentinvention, and is preferably at most 2 parts by mass, more preferably atmost 0.5 part by mass per 100 parts by mass of the working fluid.

<Heat Cycle System>

The heat cycle system of the present invention is a system employing theworking fluid of the present invention. When the working fluid of thepresent invention is applied to a heat cycle system, usually the workingfluid is applied as contained in the composition for a heat cyclesystem. The heat cycle system of the present invention may be a heatpump system utilizing heat obtained by a condenser or may be arefrigerating cycle system utilizing coldness obtained by an evaporator.

The heat cycle system of the present invention may, for example, bespecifically a refrigerator, an air-conditioning apparatus, a powergeneration system, a heat transfer apparatus and a secondary coolingmachine. Among them, the heat cycle system of the present invention,which stably exhibits heat cycle performance in a working environment athigher temperature, is preferably employed as an air-conditioningapparatus to be disposed outdoors in many cases. Further, the heat cyclesystem of the present invention is preferably employed also for arefrigerating system.

The air-conditioning apparatus may, for example, be specifically a roomair-conditioner, a package air-conditioner (such as a store packageair-conditioner, a building package air-conditioner or a plant packageair-condition, a gas engine heat pump, a train air-conditioning systemor an automobile air-conditioning system.

The refrigerator may, for example, be specifically a showcase (such as abuilt-in showcase or a separate showcase), an industrial fridge freezer,a vending machine or an ice making machine.

The power generation system is preferably a power generation system byRankine cycle system.

The power generation system may, for example, be specifically a systemwherein in an evaporator, a working fluid is heated by e.g. geothermalenergy, solar heat or waste heat in a medium-to-high temperature rangeat a level of from 50 to 200° C., and the vaporized working fluid in ahigh temperature and high pressure state is adiabatically expanded by anexpansion device, so that a power generator is driven by the workgenerated by the adiabatic expansion to carry out power generation.

Further, the heat cycle system of the present invention may be a heattransport apparatus. The heat transport apparatus is preferably a latentheat transport apparatus.

The latent heat transport apparatus may, for example, be a heat pipeconducting latent heat transport utilizing evaporation, boiling,condensation, etc. of a working fluid filled in an apparatus, and atwo-phase closed thermosiphon. A heat pipe is applied to a relativelysmall-sized cooling apparatus such as a cooling apparatus of a heatingportion of a semiconductor device and electronic equipment. A two-phaseclosed thermosiphon is widely used for a gas/gas heat exchanger, toaccelerate snow melting and to prevent freezing of roads, since it doesnot require a wick and its structure is simple.

Now, as an example of the heat cycle system according the embodiment ofthe present invention, a refrigerating cycle system will be describedwith reference to a refrigerating cycle system 10 which has been roughlydescribed above, of which the schematic construction view is shown inFIG. 3 , as an example. A refrigerating cycle system is a systemutilizing coldness obtained by an evaporator.

A refrigerating cycle system 10 shown in FIG. 3 is a system generallycomprising a compressor 11 to compress a working fluid vapor A to form ahigh temperature/high pressure working fluid vapor B, a condenser 12 tocool and liquefy the working fluid vapor B discharged from thecompressor 11 to form a low temperature/high pressure working fluid C,an expansion valve 13 to let the working fluid C discharged from thecondenser 12 expand to form a low temperature/low pressure working fluidD, an evaporator 14 to heat the working fluid D discharged from theexpansion valve 13 to form a high temperature/low pressure working fluidvapor A, a pump 15 to supply a load fluid E to the evaporator 14, and apump 16 to supply a fluid F to the condenser 12.

In the refrigerating cycle system 10, a cycle of the following (i) to(iv) is repeated.

(i) A working fluid vapor A discharged from an evaporator 14 iscompressed by a compressor 11 to form a high temperature/high pressureworking fluid vapor B (hereinafter referred to as “AB process”).

(ii) The working fluid vapor B discharged from the compressor 11 iscooled and liquefied by a fluid F in a condenser 12 to form a lowtemperature/high pressure working fluid C. At that time, the fluid F isheated to form a fluid F′, which is discharged from the condenser 12(hereinafter referred to as “BC process”).

(iii) The working fluid C discharged from the condenser 12 is expandedin an expansion valve 13 to form a low temperature/low pressure workingfluid D (hereinafter referred to as “CD process”).

(iv) The working fluid D discharged from the expansion valve 13 isheated by a load fluid E in the evaporator 14 to form a hightemperature/low pressure working fluid vapor A. At that time, the loadfluid E is cooled and becomes a load fluid E′, which is discharged fromthe evaporator 14 (hereinafter referred to as “DA process”).

The refrigerating cycle system 10 is a cycle system comprising anadiabatic isentropic change, an isenthalpic change and an isobaricchange. The state change of the working fluid, as represented on apressure enthalpy chart (curve) as shown in FIG. 6 , may be representedas a trapezoid having points A, B, C and D as vertexes.

The AB process is a process wherein adiabatic compression is carried outby the compressor 11 to change the high temperature/low pressure workingfluid vapor A to a high temperature/high pressure working fluid vapor B,and is represented by the line AB in FIG. 6 .

The BC process is a process wherein isobaric cooling is carried out inthe condenser 12 to change the high temperature/high pressure workingfluid vapor B to a low temperature/high pressure working fluid C and isrepresented by the BC line in FIG. 6 . The pressure in this process isthe condensation pressure. Of the two intersection points of thepressure enthalpy chart and the BC line, the intersection point T₁ onthe high enthalpy side is the condensing temperature, and theintersection point T₂ on the low enthalpy side is the condensationboiling point temperature. Here, the temperature glide in a case where amixture of HFO-1123, HFO-1234yf and HFC-32 is a non-azeotropic mixturefluid, is represented by the difference between T₁ and T₂.

The CD process is a process wherein isenthalpic expansion is carried outby the expansion valve 13 to change the low temperature/high pressureworking fluid C to a low temperature/low pressure working fluid D and ispresented by the CD line in FIG. 6 . T₂-T₃ corresponds to thesupercoiling degree (hereinafter referred to as “SC” as the caserequires) of the working fluid in the cycle of (i) to (iv), where T₃ isthe temperature of the low temperature/high pressure working fluid C.

The DA process is a process wherein isobaric heating is carried out inthe evaporator 14 to have the low temperature/low pressure working fluidD returned to a high temperature/low pressure working fluid vapor A, andis represented by the DA line in FIG. 6 . The pressure in this processis the evaporation pressure. Of the two intersection points of thepressure enthalpy chart and the DA line, the intersection point T₆ onthe high enthalpy side is the evaporation temperature. T₇-T₆ correspondsto the degree of superheat (hereinafter referred to as “SH” as the caserequires) of the working fluid in the cycle of (i) to (iv), where T₇ isthe temperature of the working fluid vapor A. T₄ indicates thetemperature of the working fluid D.

Here, cycle performance of the working fluid is evaluated, for example,by the refrigerating capacity (hereinafter referred to as “Q” as thecase requires) and the coefficient of performance (hereinafter referredto as “COP” as the case requires) of the working fluid. Q and COP of theworking fluid are obtained respectively in accordance with the followingformulae (1) and (2) from enthalpies h_(A), h_(B), h_(C) and h_(D) inthe respective states A (after evaporation, high temperature and lowpressure), B (after compression, high temperature and high pressure), C(after condensation, low temperature and high pressure) and D (afterexpansion, low temperature and low pressure) of the working fluid:

Q=h _(A) −h _(D)  (1)

COP=Q/compression work=(h _(A) −h _(D))/(h _(B) −h _(A))  (3)

COP means the efficiency in the refrigerating cycle system, and a higherCOP means that a higher output, for example, Q, can be obtained by asmaller input, for example, an electric energy required to operate acompressor.

Further, Q means a capacity to freeze a load fluid, and a higher Q meansthat more works can be done in the same system. In other words, it meansthat with a working fluid having a higher Q, the desired performance canbe obtained with a smaller amount, whereby the system can be downsized.

In the heat cycle system of the present invention using the workingfluid of the present invention, in a refrigerating cycle system 10 shownin FIG. 3 for example, as compared with a case where R410 (a mixed fluidof HFC-32 and HFC-125 in a mass ratio of 1:1) which has been commonlyused for an air-conditioning apparatus or the like, it is possible toachieve high levels of Q and COP, i.e. equal to or higher than those ofR410A, while remarkably suppressing the global worming potential.

Further, since the temperature glide of the working fluid contained inthe composition for a heat cycle system is suppressed to a certain levelor lower, the composition change when the composition for a heat cyclesystem is put into a refrigerator or an air-conditioning apparatus froma pressure container and a change in the refrigerant composition in arefrigerator or an air-conditioning apparatus when the refrigerant leaksout from the refrigerator or the air-conditioning apparatus, can besuppressed to lower levels. Further, since the working fluid of thepresent invention has no self-decomposition property, a heat cyclesystem employing it will operate with high durability without anyspecial measures to improve the durability.

At the time of operation of the heat cycle system, in order to avoiddrawbacks due to inclusion of moisture or inclusion of non-condensinggas such as oxygen, it is preferred to provide a means to suppress suchinclusion.

If moisture is included in the heat cycle system, a problem may occurparticularly when the heat cycle system is used at low temperature. Forexample, problems such as freezing in a capillary tube, hydrolysis ofthe working fluid or the lubricating oil, deterioration of materials byan acid component formed in the cycle, formation of contaminants, etc.may arise. Particularly, if the lubricating oil is a polyglycol oil or apolyol ester oil, it has extremely high moisture absorbing propertiesand is likely to undergo hydrolysis, and inclusion of moisture decreasesproperties of the lubricating oil and may be a great cause to impair thelong term reliability of a compressor. Accordingly, in order to suppresshydrolysis of the lubricating oil, it is necessary to control themoisture concentration in the heat cycle system.

As a method of controlling the moisture concentration in the heat cyclesystem, a method of using a moisture-removing means such as adesiccating agent (such as silica gel, activated aluminum or zeolite)may be mentioned. The desiccating agent is preferably brought intocontact with the working fluid in a liquid state, in view of thedehydration efficiency. For example, the desiccating agent is located atthe outlet of the condenser 12 or at the inlet of the evaporator 14 tobe brought into contact with the working fluid.

The desiccating agent is preferably a zeolite desiccating agent in viewof chemical reactivity of the desiccating agent and the working fluid,and the moisture absorption capacity of the desiccating agent.

The zeolite desiccating agent is, in a case where a lubricating oilhaving a large moisture absorption as compared with a conventionalmineral lubricating oil is used, preferably a zeolite desiccating agentcontaining a compound represented by the following formula (3) as themain component in view of excellent moisture absorption capacity.

M_(2/n)O·Al₂O₃ ·xSiO₂ ·yH₂O  (3)

wherein M is a group 1 element such as Na or K or a group 2 element suchas Ca, n is the valence of M, and x and y are values determined by thecrystal structure. The pore size can be adjusted by changing M.

To select the desiccating agent, the pore size and the fracture strengthare important.

In a case where a desiccating agent having a pore size larger than themolecular size of the working fluid is used, the working fluid isadsorbed in the desiccating agent and as a result, chemical reactionbetween the working fluid and the desiccating agent will occur, thusleading to undesired phenomena such as formation of non-condensing gas,a decrease in the strength of the desiccating agent, and a decrease inthe adsorption capacity.

Accordingly, it is preferred to use as the desiccating agent a zeolitedesiccating agent having a small pore size. Particularly preferred issodium/potassium type A synthetic zeolite having a pore size of at most3.5 Å. By using a sodium/potassium type A synthetic zeolite having apore size smaller than the molecular size of the working fluid, it ispossible to selectively adsorb and remove only moisture in the heatcycle system without adsorbing the working fluid. In other words, theworking fluid is less likely to be adsorbed in the desiccating agent,whereby heat decomposition is less likely to occur and as a result,deterioration of materials constituting the heat cycle system andformation of contaminants can be suppressed.

The size of the zeolite desiccating agent is preferably from about 0.5to about 5 mm, since if it is too small, a valve or a thin portion inpipelines of the heat cycle system may be clogged, and if it is toolarge, the drying capacity will be decreased. Its shape is preferablygranular or cylindrical.

The zeolite desiccating agent may be formed into an optional shape bysolidifying powdery zeolite by a binding agent (such as bentonite). Solong as the desiccating agent is composed mainly of the zeolitedesiccating agent, other desiccating agent (such as silica gel oractivated alumina) may be used in combination.

The proportion of the zeolite desiccating agent based on the workingfluid is not particularly limited.

If non-condensing gas is included in the heat cycle system, it hasadverse effects such as heat transfer failure in the condenser or theevaporator and an increase in the working pressure, and it is necessaryto suppress its inclusion as far as possible. Particularly, oxygen whichis one of non-condensing gases reacts with the working fluid or thelubricating oil and promotes their decomposition.

The non-condensing gas concentration is preferably at most 1.5 vol %,particularly preferably at most 0.5 vol % by the volume ratio based onthe working fluid, in a gaseous phase of the working fluid.

According to the above-described heat cycle system of the presentinvention, which employs the working fluid of the present inventionhaving high durability, practically sufficient heat cycle performancecan be obtained while suppressing influence over global warming, andthere is substantially no problem with respect to the temperature glide.

EXAMPLES

Now, the present invention will be described in further detail withreference to Examples. However, it should be understood that the presentinvention is by no means restricted to specific Examples. Ex. 1 to 14and 37 to 56 are Examples of the present invention, and Ex. 15 to 36 areComparative Examples. Ex. 57 is an Example of R410A (a mixed fluid ofHFC-32 and HFC-125 in a mass ratio of 1:1) used for comparativeevaluation in the following Examples of the present invention andComparative Examples, and is a Reference Example.

Ex. 1 to 56

In Ex. 1 to 32, 37 to 56, a working fluid comprising a mixture ofHFO-1123, HFO-1234yf and HFO-32 in a proportion as identified in Table 6or 7 was prepared, and the temperature glide and the refrigerating cycleperformance (refrigerating capacity Q and coefficient of performanceCOP) were measured by the following methods. In Ex. 33, 34 and 35, aworking fluid having a single composition of HFO-1123, HFO-1234yf orHFO-32 was prepared, and in Ex. 36, a working fluid comprising HFO-1123and HFO-1234uf in a mass ratio of 1.1 was prepared, and the temperatureglide and the refrigerating cycle performance (refrigerating capacity Qand coefficient of performance COP) were measured in the same manner asabove.

[Measurement of Temperature Glide and Refrigerating Cycle Performance]

The temperature glide and the refrigerating cycle performance(refrigerating capacity and coefficient of performance) were measuredwith respect to a case where the working fluid was applied to arefrigerating cycle system 10 as shown in FIG. 3 , and a heat cycle asshown in FIG. 6 , that is, adiabatic compression by a compressor 11 inthe AB process, isobaric cooling by a condenser 12 in the BC process,isenthalpic expansion by an expansion valve 13 in the CD process andisobaric heating by an evaporator 14 in the DA process, were carriedout.

Measurement was carried out by setting the average evaporationtemperature of the working fluid in the evaporator 14 to be 0° C., theaverage condensing temperature of the working fluid in the condenser 12to be 40° C., the supercooling degree (SC) of the working fluid in thecondenser 12 to be 5° C., and the degree of superheat (SH) of theworking fluid in the evaporator 14 to be 5° C. Further, it was assumedthat there was not loss in the equipment efficiency and no pressure lossin the pipelines and heat exchanger.

The refrigerating capacity and the coefficient of performance wereobtained in accordance with the above formulae (1) and (2) fromenthalpies h in the respective states of the working fluid, i.e. A(after evaporation, high temperature and low pressure), B (aftercompression, high temperature and high pressure), C (after condensation,low temperature and high pressure) and D (after expansion, lowtemperature and low pressure).

The thermodynamic properties required for calculation of the cycleperformance were calculated based on the generalized equation of state(Soave-Redlich-Kwong equation) based on the law of corresponding stateand various thermodynamic equations. If a characteristic value was notavailable, it was calculated employing an estimation technique based ona group contribution method.

The refrigerating capacity and the coefficient of performance wereobtained as relative values based on the refrigerating capacity and thecoefficient of performance of R410A measured in the same manner as abovein the after-mentioned Ex. 57 respectively being 1.000. The temperatureglide, the refrigerating capacity (relative to R410A) and thecoefficient of performance (relative to R410A) are shown in Tables 6 and7.

Working fluid composition Relative performance (relative to R410A) HFO-Coefficient of Temperature HFO-1123 1234yf HFC-32 PerformanceRefrigerating performance × glide [mass %] [mol %] [mass %] [mass %] ofcoefficient capacity refrigerating capacity [° C.] GWP Ex. 1  50 42 1040 0.965 1.123 1.083 1.6 270.6 Ex. 2  40 34 20 40 0.978 1.048 1.025 3.1270.9 Ex. 3  30 26 30 40 0.994 0.974 0.968 4.5 271.3 Ex. 4  20 18 40 401.010 0.899 0.909 5.4 271.7 Ex. 5  10 9 50 40 1.026 0.825 0.846 5.8272.0 Ex. 6  40 32 10 50 0.975 1.117 1.089 1.7 338.0 Ex. 7  30 24 20 500.989 1.042 1.031 3.1 338.4 Ex. 8  20 17 30 50 1.004 0.967 0.971 4.2338.8 Ex. 9  10 9 40 50 1.020 0.892 0.910 4.8 339.1 Ex. 10 30 23 10 600.986 1.107 1.091 1.7 405.5 Ex. 11 20 16 20 60 1.000 1.032 1.031 2.9405.9 Ex. 12 10 8 30 60 1.014 0.957 0.970 3.6 406.2 Ex. 13 20 15 10 700.996 1.093 1.088 1.6 473.0 Ex. 14 10 7 20 70 1.009 1.018 1.028 2.5473.3 Ex. 15 80 78 10 10 0.936 1.105 1.034 1.1 68.1 Ex. 16 70 70 20 100.947 1.034 0.979 2.6 68.5 Ex. 17 60 62 30 10 0.960 0.962 0.924 4.3 68.9Ex. 18 50 53 40 10 0.977 0.891 0.870 5.9 69.3 Ex. 19 40 44 50 10 0.9950.820 0.816 7.3 69.6 Ex. 20 30 34 60 10 1.013 0.747 0.757 8.2 70.0 Ex.21 20 23 70 10 1.028 0.672 0.690 8.2 70.4 Ex. 22 10 12 80 10 1.039 0.5930.617 6.9 70.7 Ex. 23 70 64 10 20 0.944 1.118 1.056 1.3 135.6 Ex. 24 6057 20 20 0.956 1.045 1.000 2.9 136.0 Ex. 25 50 48 30 20 0.971 0.9720.944 4.5 136.4 Ex. 26 40 40 40 20 0.988 0.900 0.889 6.0 136.7 Ex. 27 3031 50 20 1.006 0.827 0.832 7.1 137.1 Ex. 28 20 21 60 20 1.023 0.7530.770 7.6 137.5

Working fluid composition Relative performance (relative to R410A) HFO-Coefficient of Temperature HFO-1123 1234yf HFC-32 PerformanceRefrigerating performance × glide [mass %] [mol %] [mass %] [mass %] ofcoefficient capacity refrigerating capacity [° C.] GWP Ex. 29 10 11 7020 1.037 0.676 0.702 7.2 137.8 Ex. 30 20 19 50 30 1.016 0.828 0.842 6.6204.6 Ex. 31 10 10 60 30 1.032 0.753 0.777 6.7 204.9 Ex. 32 10  7 10 801.005 1.076 1.082 1.4 540.4 Ex. 33 100  100   0  0 0.921 1.146 1.056 00.3 Ex. 34  0  0 100   0 1.046 0.422 0.441 0 4.0 Ex. 35  0  0  0 100 1.009 1.109 1.118 0 675.0 Ex. 36 50 58 50  0 0.984 0.805 0.792 7.2 2.2Ex. 37 40 31  5 55 0.974 1.150 1.120 1.1 371.6 Ex. 38 40 33 15 45 0.9771.083 1.058 2.4 304.5 Ex. 39 40 35 25 35 0.980 1.012 0.992 3.8 237.4 Ex.40 45 35  5 50 0.969 1.155 1.119 1.0 337.8 Ex. 41 45 37 10 45 0.9701.121 1.087 1.7 304.3 Ex. 42 45 38 15 40 0.971 1.085 1.054 2.4 270.7 Ex.43 45 39 20 35 0.973 1.049 1.021 3.1 237.2 Ex. 44 50 40  5 45 0.9641.158 1.116 1.0 304.1 Ex. 45 50 43 15 35 0.966 1.087 1.049 2.3 237.0 Ex.46 55 45  5 40 0.958 1.160 1.112 0.9 270.4 Ex. 47 55 47 10 35 0.9591.124 1.078 1.6 236.8 Ex. 48 30 25 25 45 0.991 1.008 0.999 3.8 304.8 Ex.49 30 24 15 55 0.987 1.075 1.061 2.4 371.9 Ex. 50 30 22  5 65 0.9841.138 1.120 1.1 439.0 Ex. 51 35 31 30 35 0.988 0.975 0.964 4.5 237.6 Ex.52 35 30 25 40 0.986 1.011 0.996 3.8 271.1 Ex. 53 35 29 20 45 0.9841.045 1.029 3.1 304.7 Ex. 54 35 28 15 50 0.982 1.079 1.060 2.4 338.2 Ex.55 35 27 10 55 0.980 1.113 1.091 1.8 371.8 Ex. 56 35 26  5 60 0.9791.145 1.120 1.1 405.3

As evident from the results in Tables 6 and 7, the working fluids in Ex.1 to 14 and 37 to 56 having compositions within the range of the presentinvention, have a GWP and a temperature glide at low levels, have acoefficient of performance and a refrigerating capacity relative toR410A at comprehensively high levels, and have high durability, ascompared with the working fluids in Ex. 15 to 36 having compositions outof the range of the present invention, which have a high GWP or a hightemperature glide, which may undergo self-decomposition reaction ofHFO-1123, or which have a coefficient of performance and a refrigeratingcapacity relative to R410A at comprehensively low levels.

A GWP and a temperature glide at low levels and a coefficient ofperformance and a refrigerating capacity relative to R410A atcomprehensively high levels, mean a level such that all the conditionsof a GWP of at most 510, a temperature glide of less than 6.6, arelative coefficient of performance of at least 0.958 and a relativerefrigerating capacity of at least 0.820 are satisfied, and further, ifboth the relative coefficient of performance and the relativerefrigerating capacity are lower than 1.000, their product is at least0.950.

Ex. 57

In Ex. 57, with respect to R410A (a mixed fluid of HFC-32 and HFC-125 ina mass ratio of 1:1) to be relative comparison with the above Ex. 1 to56, the temperature glide and the refrigerating cycle performance(refrigerating capacity Q and coefficient of performance COP) weremeasured in the same manner as the above. The refrigerating capacity andthe coefficient of performance are 1.000 as shown in Table 8. Thetemperature glide and the result of calculation of GWP are shown inTable 8.

TABLE 8 Relative performance (relative to R410A) Temper- Working fluidCo- Refrig- ature composition [wt %] efficient of erating glide HFC-125HFC-32 performance capacity [° C.] GWP Ex. 57 50 50 1.000 1.000 0.22,087.5 (R410A)

Since R410A is a conventional working fluid, in Examples, the cycleperformance is based on this working fluid, and when the cycleperformance of a working fluid reaches the same level, the working fluidis evaluated to have practically sufficient cycle performance. R410Aconsists solely of HFCs, and has a high GWP global warming potential.

The refrigerating capacity of a working fluid is a factor whichdetermines the size of apparatus itself. If HFO-1123 is combined with acompound having a lower refrigerating capacity than HFO-1123, forexample, HFO-1234yf, the mixture (working fluid) comprising thecombination has a lower refrigerating capacity than the working fluidconsisting solely of HFO-1123. Accordingly, if such a mixture is used asan alternative to R410A, in order to make up for the low refrigeratingcapacity, an increase in the size of an apparatus itself and an increasein the energy used are required.

That is, to combine HFO-1123 and a compound having lower refrigeratingcapacity than HFO-1123 is not appropriate as a means to achieve theobjects of the present invention. Particularly under the presentcircumstances that replacement of only the working fluid is desiredwithout replacing a conventional apparatus employing R410A, an increasein the size of the apparatus is unfavorable.

However, for the working fluid of the present invention, HFO-1123 isintentionally combined with HFO-1234yf which is a compound having lowerrefrigerating capacity than HFO-1123, and further HFC-32 is added as anessential component, whereby a prescribed refrigerating capacity orhigher was achieved.

The coefficient of performance of HFO-1123 alone does not reach asufficient level, but it has a favorable relative coefficient ofperformance. The coefficient of performance indicates the efficiency ofthe working fluid and is very important considering the efficiency ofequipment.

From the viewpoint of the temperature glide, since HFC-32 and HFO-1123form an azeotropic composition or a pseudoazeotropic composition, thetendency of the temperature glide of the mixed fluid of HFO-1123,HFO-1234yf and HFC-32 is the same as the tendency of the temperatureglide of a mixed fluid of HFO-1123 and HFO-1234yf, and the temperatureglide can be suppressed to be a certain value or smaller when thecomposition range of the working fluid is within the composition rangeof the present invention, and accordingly the working fluid of thepresent invention can be used as an alternative to R410A.

As described above, it is found from the above results that in Ex. 1 to14 and 37 to 56 which are Examples of the present invention, based onR410A, the cycle performance is at a practically sufficient level. Here,HFC-32 is a compound having a high GWP. However, the working fluid ofthe present invention comprising HFC-32, and HFO-1123 and HFO-1234yfhaving extremely low GWPs in combination, has a remarkably low GWP ascompared with R410A.

Further, as described above, HFO-1123 has self-decomposition property byitself, however, the working fluid of the present invention whichcomprises HFO-1123, HFO-1234yf and HFC-32 with a composition within asufficiently practical range, has self-decomposition suppressed and hashigh durability.

According to the working fluid of the present invention, the workingfluid of the present invention having a low GWP and having highdurability can be used as an alternative to R410A working fluid withoutreplacement of equipment, and the present invention is useful under suchpresent circumstances.

INDUSTRIAL APPLICABILITY

The working fluid of the present invention is useful as a refrigerantfor a refrigerator (such as a built-in showcase, a separate showcase, anindustrial fridge freezer, a vending machine or an ice making machine),a refrigerant for an air-conditioning apparatus (such as a roomair-conditioner, a store package air-conditioner, a building packageair-conditioner, a plant package air-conditioner, a gas engine heatpump, a train air-conditioning system or an automobile air-conditioningsystem), a working fluid for power generation system (such as exhaustheat recovery power generation), a working fluid for a heat transportapparatus (such as a heat pipe) or a secondary cooling fluid.

This application is a continuation of PCT Application No.PCT/JP2015/052533 filed on Jan. 29, 2015, which is based upon and claimsthe benefit of priority from Japanese Patent Application No. 2014-017031filed on Jan. 31, 2014 and Japanese Patent Application No. 2014-148350filed on Jul. 18, 2014. The contents of those applications areincorporated herein by reference in their entireties.

REFERENCE SYMBOLS

-   10: refrigerating cycle system, 11: compressor, 12: condenser, 13:    expansion valve, 14: evaporator, 15, 16: pump.

1-8. (canceled)
 9. A working fluid for a heat cycle, comprising:trifluoroethylene; and difluoromethane; wherein: the working fluidexhibits a pressure change of 0.00 and a temperature change of 0.5° C.or less in an evaluation of self-decomposition; and the evaluation ofself-decomposition is conducted by: enclosing a sample of the workingfluid and a platinum wire in a spherical pressure resistant reactorhaving an internal capacity of 650 cm³ at a temperature is 250° C. and apressure of 0.98 MPaG; fusing the platinum wire to apply an energy ofabout 30 J to the working fluid; and measuring the temperature changeand pressure change in the pressure resistant reactor after applyingenergy to the working fluid.
 10. The working fluid according to claim 9,wherein: trifluoroethylene is present in an amount of 80 mass % or lessbased on a total mass of trifluoroethylene and difluoromethane; anddifluoromethane is present in an amount of 20 mass % of more based onthe total mass of trifluoroethylene and difluoromethane.
 11. The workingfluid according to claim 9, wherein: trifluoroethylene is present in anamount of 70 mass % or less based on a total mass of trifluoroethyleneand difluoromethane; and difluoromethane is present in an amount of 30mass % of more based on the total mass of trifluoroethylene anddifluoromethane.
 12. The working fluid according to claim 9, wherein aGlobal Warming Potential (GWP) of the working fluid is 300 or less. 13.A composition for a heat cycle system, comprising the working fluidaccording to claim 9 and a lubricating oil.
 14. A heat cycle system,comprising the composition according to claim
 13. 15. The heat cyclesystem according to claim 14, wherein the heat cycle system is at leastone selected from the group consisting of a refrigerating apparatus, anair-conditioning apparatus, a power generation system, a heat transportapparatus, and a secondary cooling machine.
 16. The heat cycle systemaccording to claim 14, wherein the heat cycle system is at least oneselected from the group consisting of a room air-conditioner, a storepackage air-conditioner, a building package air-conditioner, a plantpackage air conditioner, a gas engine heat pump, a trainair-conditioning system, an automobile air-conditioning system, abuilt-in showcase, a separate showcase, an industrial fridge freezer, anice making machine, and a vending machine.